Vinyloxyaryl sulphonic acids and polymers thereof



M 3,949,512 Famed latter dice United States Patent 1 3,049,512 I VDIYLDXYARYL SULPHQNIC ACIDS AYE) POLYMERS THEREOF Andre Foul-net and Hubert Lemoine, Lyon, France, as signor s to Societe -des Usines Chimiques Rhone- Poulenc, Paris, France, a body corporate or France NoDrawing. FiledFeb. 2,1960, Seia'No. 7,5 3. Claims priority, appiication'France' Feb. 11, 1959 7 ;Claim. s. (Cl. 260-49) This invention relates to vinyl derivatives'and more particularly to the provision of a new class of vinyl derivatives, to theirpr oduction and to the production of polym and; copolyme s the eof... 7

A co i g 19.1 1: Pr sent nve on there are p i vinyl derivatives of the general Formula I:

cH cH o Asmm 1 Hal.CH .CH .O.Ai-' where Hal is a halogen atom and Ar has the meaning assigned to it above, and subjecting the products to treatment with alkali metal hydroxide. ethoxy-aryl sulphonic acids obtained as intermediates,

when subjected to the action of an aqueous solution of an alkali metal hydroxide, lose one molecule of hydro-.

gen halide and are converted into alkali salts of vinyloxyaryl-sulphonic acids, from which the corresponding acids or esters can be prepared by methods known per se.

Compounds of generaLEormula II may be prepared by known methods, for example by the action of a dihalogenoethan, more especially dibromoethane, on a hydroxyaryl compound in the presence of alkali. The sulphonation may be effected, for example, by the action of hot concentrated sulphuric acid or by treatment with any other sulphonating agent known per se. Depending upon the operating conditions, one or more sulphonic groups are introduced into the aromatic nucleus.

The aromatic group may be derived from benzene and its alkylated or cycloalkylated homologues, or from polycyclic hydrocarbons, such as diphenyl, naphthalene or anthracene, and their alkylated homologues. Any of such groups may carry halogen substituent groups.

Owing to the presence of the vinyl group, the compounds of general Formula I according to the invention may be polymerised and the present invention accordingly further includes homopolymers thereof and copolymers thereof with other unsaturated derivatives such as olefines, diolefines, vinylaromatic derivatives, vinyl ethers and esters, vinyl ketones, unsaturated acids and their esters, amides and nitriles, and unsaturated nitrogen derivatives,

The alkali metal salts of homopolymers of the vinyloxyaryl sulphonic acids of general Formula I are soluble in water, as also are the copolymers containing high proportions of vinyloxyaryl sulphonic acids. mers and copolymers can be used as emulsifiers. The presence of sulphonic groupings in those copolymers which are not soluble in water imparts to these copolymers hydrophilic properties and an afiinity for basic dyes.

The B-halogeno- These poly- Thus copolymers of the vinyloxyaryl 'sulphonic-iacid's of general Formula I with acrylonitrile, may be dyed basic dyes and this forms. a particularly valuable feature 0f the invention. It is generally sufiicient to copolymer ise with acrylonitrile a small'proportion of'vinyloxyaryl sulphonic acid, e.g. from 0.5% to 2%, in order to impart to the polymer obtained anexcellenhdye affinity. It is also possible to prepare copolymers'having-ahigher proportion of vinyloxyaryl sulphonic acids, for example from 2% to 15%, and if desired to mix from .5.%..to .25 of these polymers with homopolymers or cgpolyrners of acrylonitrile.

It has tturther been found that by includingiasla third component in the copolymerisat-ion-mixtureof acrylonitrile and vinyloxyaryl sulphonic acid; ana'crylic ormethacrylic ester, such as methyl, ethyL'bu'tyl or'ethylhexyl esters, it is possible to improve the; dyeability and to widen the range of dyes which may be employed. The said third component may usefully befeniployed in a proportion of from 1% to l0% of the mixture? The polymerisation is preferably carried outin aqueous medium in which the alkali salts of the'vinyl'oxyaryl sul phonic acids are soluble. The monomer or mixture of monomers is dissolved or dispersed in this medium and a conventional polymerisation catalyst is added.

The following examples willserve .to .illustrate..the ill-f vention. 'Parts, given are by weight...

EXAMPLE I "Preparation of Sodium Vinyloxyl enxene Szilphorizite A mixture consisting of 785 g. or entioned at bromoethane and 2 litres ofywater is,heated--;to boiling point, and 375 g. of sodium hydroxide is;then added. 970 g. of Babromoethoxybenzene, are thus obtained. ,1 Y

. The fi-bromoethoxybenzene obtained is thereafter sulphonated by heating at 100 C. for 3 hourswith sul-,

phuric acid (66 B.) in a proportion of 1.1 mols of sulphuric acid to 1 mol of bromoethoxybenzene. After cooling, the mixture is diluted. with cc. .ofwater per:

mol of B-bromoethoxybenzene and the: product is then neutralised at 15 to 25 C., with sodium hydroxide solution (36 B.) Sodium B-bromoethoxybenzene-sulphonate is thus obtained in a yield of 90%. Q

To a solution of 2 mol. of this salt'in 1090 cc. orbit r,

heated at 85 C., is added, dropby-drop during 30min: utes and with agitation, a'sodium hydroxide solution obtained by dissolving 2.4 mol. of sodium hydroxide in cc. of Water. After agitation for 1 /2 hoursat 85" C., sodium vinloxybenzene sulphonateis obtained-in "a yield of 96.2%. On cooling,vthe,alkali.salt crystallises. It is purified by recrystallisation. i I

The sodium yinyloxybenzene-sulphonate in aqueous solution without risk of polymerisation proof the solutionis maintained between,

vided that the pH 7 and 9.

It is not necessary to isolate the zene sulphonate when it is required to make polymers, or

copolymers therefrom; for such purposes the solution ob tained after the dehydrobromination step may be erncombined monomers represent a concentration of"l0 by weight. The mixture is brought to a pH of 2:5;byfthe addition of sulphuric acid and heated in an inertatmosphere to 42 C. 1.62 parts of. sodiumbisulphite and 0.5

Pa.rt 0f Potassium a te 9 Par simgnomers.

are then introduced. The quantity of such catalysts is voluntarily limited so as not to exceed a degree of conversion of 60-70% which is :favourable to the production of a polymer having a low degree of branching. The polymerisation is ended in 20 minutes. After elumination of the unreacted monomers by washing, followed by drying, copolymers are obtained which have the characteristics given in the following table.

Sulphonated Acrylonitrile Degree of Specific Test N o. derivative (Percent by conversion, viscosity (Percent by weight) percent Weight) Films are prepared from these polymers and dyed with the dyestulf malachite green. While the film obtained with the product of Test No. l, i.e. the homopolymer of acrylonitrile, only acquires a taint green shade, there is observed with a proportion of 0.59% of sulphonated derivative an improvement in the dyeing which increases as the proportion of sulphonated derivative is increased.

EXAMPLE I I I Copolymerisation of Potassium VinyIoxybenzene-Sulphonate With a Mixture of Acrylonitrile and Methyl Methacrylate The procedure of Example II is followed, but a part of the acrylonitrile is replaced by methyl methacrylate.

With a proportion of 92.6% of acrylonitrile, 5% of methyl methacrylate and 2.4% of potassium vinyloxybenzene-sulphonate, there is obtained a copolymer having a specific viscosity of 0.284 with a degree of conversion of 65%. The copolymer obtained has a very high dye afiinity.

EXAMPLE IV Continuous Copolymerisatzlon of Sodium Vinyloxybenzene-Sulphonate With a Mixture of Acrylonitrile and Methyl Methaorylate Into -a 16-litre reactor provided with an overflow and a screw-type stirrer, in which the atmosphere consists of an inert gas, are introduced:

11.900 litres of de-ionised distilled water.

1260 grams of acrylonitrile.

19.5 grams of sodium vinyloxybenzene-sulphonate. 14 grams of methyl methacrylate.

1180 grams of a mixture consisting of 94.7% by weight of acrylonitrile and 5.3% by weight of methyl methacrylate.

3160 grams of an aqueous 1.32/ by weight potassium chlorate solution.

3160 grams of an aqueous 4.3/ by weight sodium bisulp'hite solution, and

500 grams of an aqueous by weight sodium vinyloxybenzene-sulphonate solution maintained at a pH of 8.5.

The mean time for which the reactants remain in the reactor is thus about 2 hours. Throughout the reaction,

an inert atmosphere and a temperature of 60 C. are maintained in the reactor. The pH remains at 2.3-2.4. The polymer suspension which leaves the reactor enters an evaporator heated to eliminate the unreacted acrylonitrile and methyl methacrylate. The extent of the conversion is 71% calculated on the total weight of the monomers. The polymer is washed with water, separated and dried.

The copolymer obtained contains approximately 92% of acrylonitrile, 6.5% of methyl methacrylate and 1.5% of vinyloxybenzene-sulphonic acid. It has a specific viscosity of 0.41.

The copolymer is converted into fibre and is subjected to a dyeing test. For this purpose, there are dissolved in cc. of water:

Emulsifying agent cc 0.1 Acetic acid cc 0.1 Sodium acetate g 0.15

and then, at 70% C., with agitation, the dyestuif Bleu Astrazon g 0.06

2 g. of degreased fibres are immersed in this bath and maintained for 1 hour at boiling point.

The light absorption of the solution before and after dyeing is photometrically measured and shows that the dye absorption is 81%. Under the same conditions, an acrylonitrile-methyl-methacrylate copolymer prepared in the absence of vinyloxybenzene-sulphonic acid has a dye absorption of only 30-34%.

We claim:

1. A vinyl derivative of the general formula:

where Ar is a group selected from the class consisting of wholly aromatic unsubstituted hydrocarbon groups, aromatic hydrocarbon groups containing alkyl substituents, aromatic hydrocanbon groups containing cycloalkyl substituents and aromatic hydrocarbon groups containing halogen substituents and R is selected from the class consisting of the hydrogen atom, metal atoms and hydrocarbon groups.

4. A copolymer of acrylonitrile with a vinyl derivative of the general formula:

where Ar is a group selected from the class consisting of wholly aromatic unsubstituted hydrocarbon groups, aromatic hydrocarbon groups containing alkyl substituents, aromatic hydrocarbon groups containing cycloalkyl substituents and aromatic hydrocarbon groups containing halogen substituents and R is selected from the class consisting of the hydrogen atom, metal atoms and hydrocarbon groups.

5. A copolymer of acrylonitrile and methyl methacrylate with a vinyl derivative of the general formula:

where Ar is a group selected from the class consisting of wholly aromatic unsubstituted hydrocarbon groups, aromatic hydrocarbon groups containing alkyl substituents, aromatic hydrocarbon groups containing cycloalkyl sub stituents and aromatic hydrocarbon groups containing halogen substituents and R is selected from the class consisting of the hydrogen atom, metal atoms and hydrocarbon groups.

6. A copolymer of acrylonitrile with a vinyl derivative of the general formula:

where AI is a group selected from the class consisting of WhOllY aromatic unsubstituted hydrocarbon groups, aromatic hydrocarbon groups containing alkyl substituents, aromatic hydrocarbon groups containing cycloalkyl substituents and aromatic hydrocarbon groups containing halogen substituents and R is selected vfrom the class consisting of the hydrogen atom, metal atoms and hydrocarbon groups, wherein the compound of the said formula constitutes 0.5 to 15% by Weight of the copolymer.

7. A copolymer of acrylonitrile and methyl methacrylate With a vinyl derivative of the general formula:

Where AI is a group selected :from the class consisting of Wholly aromatic unsubstituted hydrocarbon groups, aromatic hydrocarbon groups containing alkyl substituents, aromatic hydrocarbon groups containing cycloalkyl substituents and aromatic hydrocarbon groups containing halogen substituents and R is selected from the class consisting of the hydrogen atom, metal atoms and hydrocarbon groups, Wherein the compound of the said formula constitutes 0.5 to 15% by Weight of the copolymer and the methyl methacrylate constitutes l to 10% by Weight of the copolymer.

References Cited in the file of this patent UNITED STATES PATENTS 2,205,946 Elitt June 25, 1940 2,527,300 Dudley Oct. 24, 1950 2,836,578 Teot May 27, 1958 

1. A VINYL DERIVATIVE OF THE GENERAL FORMULA: 